Process for making and composition of superior lubricant or lubricant blendstock

ABSTRACT

A process for making and a composition of a superior lubricant or lubricant component by the oligomerization of a mixture comprising olefins and isoparaffins to produce an alkylated (“capped”) olefin oligomer having a very high VI and a low cloud point. The process preferably uses an acidic chloroaluminate ionic liquid catalyst system. Preferably the ionic liquid catalyst system comprises a Brönsted acid.

BACKGROUND OF THE INVENTION

Olefin oligomers and relatively long chain olefins can be used in theproduction of high value lubricant components or blendstocks. Oneproblem with the use of olefin oligomers in either of the above uses isthat the olefinic double bond can be undesirable. Olefinic double bondscause problems in both fuels and in lubricants. Olefin oligomers canfurther oligomerize forming ‘gum’ deposits in the fuel. Olefins in fuelare also associated with air quality problems. Olefins can also oxidizewhich can be a particular problem in lubricants. One way of minimizingthe problem is to hydrogenate some or all of the double bonds to formsaturated hydrocarbons. A method of doing this is described in U.S.published Application U.S. 2001/0001804 which is incorporated herein inits entirety. Hydrogenation can be an effective way to minimize theconcentration of olefins in the lubricant or fuel however it requiresthe presence of hydrogen and a hydrogenation catalyst both of which canbe expensive. Also excessive hydrogenation can lead to hydrocracking.Hydrocracking can increase as one attempts to hydrogenate the olefins toincreasingly lower concentrations. Hydrocracking is generallyundesirable as it produces a lower molecular weight material where thegoal in oligomerization is to produce a higher molecular weightmaterial. Directionally it would generally be preferred to increase, notdecrease the average molecular weight of the material. Thus using thehydrogenation method it is desired to hydrogenate the olefins asthoroughly as possible while minimizing any hydrocracking orhydrodealkylation. This is inherently difficult and tends to be acompromise.

Hydrocracking of a slightly branched hydrocarbon material can also leadto less branching. Cracking tend to be favored at the tertiary andsecondary centers. For example a branched hydrocarbon can crack at asecondary center forming two more linear molecules which is alsodirectionally undesirable.

Potentially, Ionic Liquid catalyst systems can be used for theoligomerization of olefins such as normal alpha olefins to make olefinoligomers. A Patent that describes the use of an ionic liquid catalystto make polyalphaolefins is U.S. Pat. No. 6,395,948 which isincorporated herein by reference in its entirety. A publishedapplication that discloses a process for oligomerization of alphaolefins in ionic liquids is EP 791,643.

Ionic Liquid catalyst systems have also been used for isoparaffin—olefinalkylation reactions. Patents that disclose a process for the alkylationof isoparaffins by olefins are U.S. Pat. No. 5,750,455 and U.S. Pat. No.6,028,024.

It would be desirable to have a process for making a lubricant orlubricant starting materials with low degree of unsaturation (lowconcentration of double bonds) thus reducing the need for exhaustivehydrogenation while preferably maintaining or more preferably increasingthe average molecular weight and branching of the material while alsoincreasing the lubricant properties of the product. The presentinvention provides a new process and a new composition with just suchdesired features.

SUMMARY OF THE INVENTION

The present invention provides a process for making a lubricant orlubricant component by the oligomerization of olefins to make olefinoligomers of desired chain length range and by alkylation of the olefinoligomer with an isoparaffin to “cap” (alkylate) at least a portion ofthe remaining double bonds of the olefin oligomers.

A particular embodiment of the present invention provides a process formaking a lubricant or lubricant component, comprising, oligomerizing afeed comprising one or more olefins in an ionic liquid oligomerizationzone, at oligomerization conditions, to form an oligomer; alkylatingsaid oligomer in the presence of an isoparaffin, in an ionic liquidalkylation zone, at alkylation conditions, to form an alkylatedoligomeric product having a cloud point less than −50 degrees C., aViscosity Index of at least 134, and a difference between the T90 andT10 boiling points of at least 225 degrees F. by Simulated Distillation(SIMDIST). In a particular embodiment the oligomerization can occursimultaneously with the alkylation (i.e. the oligomerization zone andthe alkylation zone are the same) or the oligomerization and thealkylation can occur in different zones preferably under optimizedconditions for each zone.

In another embodiment of the present invention, a lubricant component orbase oil is disclosed, comprising, a cloud point of less than −50degrees C.; a Viscosity Index of at least 134; a difference between theT90 and T10 boiling points of at least 300 degrees F. by SIMDIST; and aBromine Number of less than 0.2.

Oligomerization of two or more olefin molecules results in the formationof an olefin oligomer that generally comprises a long branched chainmolecule with one remaining double bond. The present invention providesa novel way to reduce the concentration of double bonds and at the sametime enhance the quality of the desired fuel or lubricant. Thisinvention also reduces the amount of hydrofinishing that is needed toachieve a desired product with low olefin concentration. The olefinconcentration can be determined by Bromine Index or Bromine Number.Bromine Number can be determined by test ASTM D 1159. Bromine Index canbe determined by ASTM D 2710. Test methods D 1159 and ASTM D 2710 areincorporated herein by reference in their entirety. Bromine Index iseffectively the number of milligrams of Bromine (Br₂) that react with100 grams of sample under the conditions of the test. Bromine Number iseffectively the number of grams of bromine that will react with 100grams of specimen under the conditions of the test.

In a preferred embodiment of the present invention, HCl or a componentthat directly or indirectly supplies protons is added to the reactionmixture. Although not wishing to be limited by theory it is believedthat the presence of a Brönsted acid such as HCl greatly enhances theacidity and, thus, the activity of the ionic liquid catalyst system.

Among other factors, the present invention involves a surprising new wayof making a lubricant base oil or lubricant blendstock that has reducedlevels of olefins without hydrogenation or with minimal hydrofinishing.The present invention also increases the value of the resultant olefinoligomers by increasing the molecular weight of the oligomer andincreasing the branching by incorporation of isoparaffin groups into theoligomers' skeletons. These properties can both add significant value tothe product particularly when starting with a highly linear hydrocarbonsuch as the preferred feeds to the present invention (i.e.Fischer-Tropsch derived hydrocarbons). The product of the presentinvention can have a combination of highly desirable and novel qualitiesfor a lubricant component or base oil including a very high ViscosityIndex with a very low cloud point while having a fairly wide boilingrange. The present invention is based on the use of an ionic liquidcatalyst to alkylate an oligomerized olefin with an isoparaffin underrelatively mild conditions. The alkylation optionally can occur undereffectively the same conditions as oligomerization. This finding thatalkylation and oligomerization reactions can occur using effectively thesame ionic liquid catalyst system and optionally under similar or eventhe same conditions can be used to make a highly integrated, synergisticprocess resulting in an alkylated oligomer product having desirableproperties. Also in a particular embodiment of the present invention thealkylation and oligomerization reactions can occur simultaneously underthe same conditions.

A preferred catalyst system of the present invention is an acidicchloroaluminate ionic liquid system. More preferably the acidicchloroaluminate ionic liquid system is used in the presence of aBrönsted acid. Preferably the Brönsted acid is a halohalide and mostpreferably is HCl.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a novel process for the production oflubricant or lubricant components by the acid catalyzed oligomerizationof olefins and alkylation with isoparaffins in ionic liquid medium toform a product having greatly reduced olefin content and improvedquality. Amazingly, we found that oligomerization of an olefin andalkylation of an olefin and/or its oligomers with an isoparaffin can beperformed together in a single reaction zone or alternatively in twoseparate zones. The alkylated or partially alkylated oligomer streamthat results has very desirable properties for use as a lubricant orlubricant blendstock. In particular the present invention provides aprocess for making a lubricant, base oil, lubricant component, orsolvent having improved properties such as increased branched, highermolecular weight, and low Bromine Number. The present invention alsoprovides a composition of a lubricant component or base oil havingimproved properties including a cloud point of less than −55 degrees C.;a Viscosity Index of at least 140; a difference between the T90 and T10boiling points of at least 250 degrees F. by SIMDIST; and a BromineNumber of less than 0.2.

As mentioned the oligomerization reaction and the alkylation reaction inthe present invention can be performed together or separately. Anadvantage of combining the oligomerization and alkylation is lowercapital and operating costs. An advantage of the 2 step process(oligomerization followed by alkylation in a separate zone) is that thetwo separate reaction zones can be optimized independently. Thus theconditions for oligomerization zones can be different than thealkylation zone conditions. Also the ionic liquid catalyst can bedifferent in the different zones. For instance, it may be preferable tomake the alkylation zone more acidic than the oligomerization zone. Thismay involve the use of an entirely different ionic liquid catalyst inthe two zones or can be by addition of a Brönsted acid to the alkylationzone.

In a preferred embodiment of the present invention, the ionic liquidused in alkylation zone and in the oligomerization zone is the same.This helps save on catalyst costs, potential contamination issues, andprovides synergy opportunities in the process.

As discussed above, the present invention produces a product having avery low cloud point and a very high Viscosity Index (VI). Cloud Pointcan be determined by ASTM D 2500. Viscosity Index can be determined byASTM D 2270. ASTM test methods D 2500 and D D2270 are incorporated byreference herein in their entirety.

In the present application, distillation data was generated for severalof the products by SIMDIST. Simulated Distillation (SIMDIST) involvesthe use of ASTM D 6352 or ASTM D 2887 as appropriate. ASTM D 6352 andASTM D 2887 are incorporated herein by reference in their entirety.Distillation data can also be generated using ASTM D86 which isincorporated herein by reference in its entirety.

In the present application the terms lubricant base oil, lubricantblendstock, and lubricant component are used to mean lubricantcomponents that can be used to produce a finished lubricant.

Ionic Liquids

Ionic liquids are a class of compounds made up entirely of ions and aregenerally liquids at ambient and near ambient temperatures. Often saltswhich are composed entirely of ions are solids with high melting points,for example, above 450 degrees C. These solids are commonly known as‘molten salts’ when heated to above their melting points. Sodiumchloride, for example, is a common ‘molten salt’, with a melting pointof 800 degree C. Ionic liquids differ from ‘molten salts’, in that theyhave low melting points, for example, from −100 degrees C. to 200 degreeC. Ionic liquids tend to be liquids over a very wide temperature range,with some having a liquid range of up to 300 degrees C. or higher. Ionicliquids are generally non-volatile, with effectively no vapor pressure.Many are air and water stable, and can be good solvents for a widevariety of inorganic, organic, and polymeric materials.

The properties of ionic liquids can be tailored by varying the cationand anion pairing. Ionic liquids and some of their commercialapplications are described, for example, in J. Chem. Tech. Biotechnol,68:351-356 (1997); J. Phys. Condensed Matter, 5:(supp 34B):B99-B106(1993); Chemical and Engineering News, Mar. 30, 1998, 32-37; J. Mater.Chem., *:2627-2636 (1998); and Chem. Rev., 99:2071-2084 (1999), thecontents of which are hereby incorporated by reference.

Many ionic liquids are amine-based. Among the most common ionic liquidsare those formed by reacting a nitrogen-containing heterocyclic ring(cyclic amines), preferably nitrogen-containing aromatic rings (aromaticamines), with an alkylating agent (for example, an alkyl halide) to forma quaternary ammonium salt, followed by ion exchange with Lewis acids orhalide salts, or by anionic metathesis reactions with the appropriateanion sources to introduce the desired counter anionic to form ionicliquids. Examples of suitable heteroaromatic rings include pyridine andits derivatives, imidazole and its derivatives, and pyrrole and itsderivatives. These rings can be alkylated with varying alkylating agentsto incorporate a broad range of alkyl groups on the nitrogen includingstraight, branched or cyclic C₁₋₂₀ alkyl group, but preferably C₁₋₁₂alkyl groups since alkyl groups larger than C₁-C₁₂ may produceundesirable solid products rather than ionic liquids. Pyridinium andimidazolium-based ionic liquids are perhaps the most commonly used ionicliquids. Other amine-based ionic liquids including cyclic and non-cyclicquaternary ammonium salts are frequently used. Phosphonium andsulphonium-based ionic liquids have also been used.

Counter anions which have been used include chloroaluminate,bromoaluminate, gallium chloride, tetrafluoroborate, tetrachloroborate,hexafluorophosphate, nitrate, trifluoromethane sulfonate,methylsulfonate, p-toluenesulfonate, hexafluoroantimonate,hexafluoroarsenate, tetrachloroaluminate, tetrabromoaluminate,perchlorate, hydroxide anion, copper dichloride anion, iron trichlorideanion, antimony hexafluoride, copper dichloride anion, zinc trichlorideanion, as well as various lanthanum, potassium, lithium, nickel, cobalt,manganese, and other metal ions. The ionic liquids used in the presentinvention are preferably acidic haloaluminates and preferablychloroaluminates.

The organic cations in the ionic liquid of the present invention can beselected from the group consisting of pyridinium-based andimidazolium-based cations. Cations that have been found to beparticularly useful in the process of the present invention includepyridinium-based cations.

Preferred ionic liquids that can be used in the process of the presentinvention include acidic chloroaluminate ionic liquids. Preferred ionicliquids used in the present invention are acidic pyridiniumchloroaluminates. More preferred ionic liquids useful in the process ofthe present invention are alkyl-pyridinium chloroaluminates. Still morepreferred ionic liquids useful in the process of the present inventionare alkyl-pyridinium chloroaluminates having a single linear alkyl groupof 2 to 6 carbon atoms in length. One particular ionic liquid that hasproven effective is 1-butyl-pyridinium chloroaluminate.

In a more preferred embodiment of the present invention1-butyl-pyridnium chloroaluminate is used in the presence of a Brönstedacid. Not to be limited by theory, the Brönsted acid acts as a promoteror co-catalyst. Examples of Brönsted acids are Sulfuric, HCl, HBr, HF,Phosphoric, HI, etc. Other protic acids or species that directly orindirectly aid in supplying protons may also be used as Bronsted acidsor in place of Brönsted acids.

The Feeds

In the process of the present invention one of the important feedstockscomprises a reactive olefinic hydrocarbon. The olefinic group providesthe reactive site for the oligomerization reaction as well as thealkylation reaction. The olefinic hydrocarbon can be a fairly pureolefinic hydrocarbon cut or can be a mixture of hydrocarbons havingdifferent chain lengths thus a wide boiling range. The olefinichydrocarbon can be terminal olefin (an alpha olefin) or can be internalolefin (internal double bond). The olefinic hydrocarbon chain can beeither straight chain or branched or a mixture of both. The feedstocksuseable in the present invention can include unreactive diluents such asnormal paraffins.

In one embodiment of the present invention, the olefinic feed comprisesa mixture of mostly linear olefins from C₂ to about C₃₀. The olefins aremostly but not entirely alpha olefins.

In another embodiment of the present invention, the olefinic feed cancomprise at least 50% of a single alpha olefin species.

In another embodiment of the present invention, the olefinic feed can becomprised of an NAO cut from a high purity Normal Alpha Olefin (NAO)process made by ethylene oligomerization.

In an embodiment of the present invention, some or all of the olefinicfeed to the process of the present invention comprises thermally crackedhydrocarbons, preferably cracked wax, and more preferably cracked waxfrom a Fischer-Tropsch (FT) process. A process for making olefins bycracking FT products is disclosed in U.S. Pat. No. 6,497,812 which isincorporated herein by reference in its entirety.

In the process of the present invention, another important feedstock isan isoparaffin. The simplest isoparaffin is isobutane. Isopentanes,isohexanes, isoheptanes, and other higher isoparaffins are also useablein the process of the present invention. Economics and availability arethe main drivers of the isoparaffins selection. Lighter isoparaffinstend to be less expensive and more available due to their low gasolineblend value (due to their relatively high vapor pressure). Mixtures oflight isoparaffins can also be used in the present invention. Mixturessuch as C₄-C₅ isoparaffins can be used and may be advantaged because ofreduced separation costs. The isoparaffins feed stream may also containdiluents such as normal paraffins. This can be a cost savings byreducing the cost of separating isoparaffins from close boilingparaffins. Normal paraffins will tend to be unreactive diluents in theprocess of the present invention.

In an optional embodiment of the present invention the resultantalkylated oligomer made in the present invention can be hydrogenated tofurther decrease the concentration of olefins and thus the BromineNumber. After hydrogenation the lubricant component or base oil has aBromine Number of less than 0.8, preferably less than 0.5, morepreferably less than 0.3, still more preferably less than 0.2.

Alkylation conditions for the process of the present invention include atemperature of from about 15 to about 200 degrees C., preferably fromabout 20 to about 150 degrees C., more preferably from about 25 to about100, and most preferably from 50 to 100 degrees C.

Oligomerization conditions for the process of the present inventioninclude a temperature of from about 0 to about 150 degrees C.,preferably from about 10 to about 100 degrees C., more preferably fromabout 0 to about 50.

As discussed elsewhere in the present application the oligomerizationand the alkylation can occur separately (in separate optimized zones) orcan occur together. In the embodiment where the alkylation andoligomerization occur together, optimum conditions for either reactionmay have to be compromised. However, surprisingly the conditions can beadjusted to achieve both substantial oligomerization and alkylation andresulting in a valuable lubricant base oil or blendstock.

In summary, the potential benefits of the process and composition of thepresent invention include:

-   -   Reduced capital cost for hydrotreating/hydrofinishing    -   Lower operating cost due to reduced hydrogen and extensive        hydrogenation requirements    -   Potential use of the same ionic liquid catalyst for        oligomerization and alkylation steps    -   Improved branching characteristics of the product    -   Increased overall molecular weight of the product    -   Incorporation of low cost feed (isoparaffins) to increase liquid        yield of high value distillate fuel or lubricant components    -   Production of a base oil or lubricant component having unique,        high value properties

EXAMPLES Example 1 Preparation of Fresh 1-Butyl-PyridiniumChloroaluminate Ionic Liquid

1-butyl-pyridinium chloroaluminate is a room temperature ionic liquidprepared by mixing neat 1-butyl-pyridinium chloride (a solid) with neatsolid aluminum trichloride in an inert atmosphere. The syntheses of1-butyl-pyridinium chloride and the corresponding 1-butyl-pyridiniumchloroaluminate are described below. In a 2-L Teflon-lined autoclave,400 gm (5.05 mol.) anhydrous pyridine (99.9% pure purchased fromAldrich) were mixed with 650 gm (7 mol.) 1-chlorobutane (99.5% purepurchased from Aldrich). The neat mixture was sealed and let to stir at125° C. under autogenic pressure over night. After cooling off theautoclave and venting it, the reaction mix was diluted and dissolved inchloroform and transferred to a three liter round bottom flask.Concentration of the reaction mixture at reduced pressure on a rotaryevaporator (in a hot water bath) to remove excess chloride, un-reactedpyridine and the chloroform solvent gave a tan solid product.Purification of the product was done by dissolving the obtained solidsin hot acetone and precipitating the pure product through cooling andaddition of diethyl ether. Filtering and drying under vacuum and heat ona rotary evaporator gave 750 gm (88% yields) of the desired product asan off-white shinny solid. ¹H-NMR and ¹³C-NMR were ideal for the desired1-butyl-pyridinium chloride and no presence of impurities was observedby NMR analysis.

1-Butyl-pyridinium chloroaluminate was prepared by slowly mixing dried1-butyl-pyridinium chloride and anhydrous aluminum chloride (AlCl₃)according to the following procedure. The 1-butyl-pyridinium chloride(prepared as described above) was dried under vacuum at 80° C. for 48hours to get rid of residual water (1-butyl-pyridinium chloride ishydroscopic and readily absorbs water from exposure to air). Fivehundred grams (2.91 mol.) of the dried 1-butyl-pyridinium chloride weretransferred to a 2-Liter beaker in a nitrogen atmosphere in a glove box.Then, 777.4 gm (5.83 mol.) of anhydrous powdered AlCl₃ (99.99% fromAldrich) were added in small portions (while stirring) to control thetemperature of the highly exothermic reaction. Once all the AlCl₃ wasadded, the resulting amber-looking liquid was left to gently stirovernight in the glove box. The liquid was then filtered to remove anyun-dissolved AlCl₃. The resulting acidic 1-butyl-pyridiniumchloroaluminate was used as the catalyst for the Examples in the PresentApplication.

Example 2 Oligomerization of 1-Decene

One process for making high quality oils is by oligomerization ofolefins followed in a separate step by alkylation with an isoparaffin.Olefin oligomers exhibit good physical lubricating properties. However,introducing short chain branching in the oligomers enhances theproperties of the final products. Introducing the branching can be doneby alkylation of the oligomers with isoparaffins. Alkylation of theoligomeric products is also a route to reducing the olefinicity of theoligomers and, hence, producing chemically and thermally more stableoligomers. The process is exemplified by alkylation of 1-deceneoligomers (described below).

Oligomerization of 1-decene and alkylation of the oligomer were doneaccording to the procedures described below. In a 300 cc autoclaveequipped with an overhead stirrer, 100 gm of 1-decene was mixed in with20 gm of 1-methyl-tributyl ammonium chloroaluminate. A small amount ofHCl (0.35 gm) was introduced to the mix as a promoter and the reactionmix was heated to 50° C. with vigorous stirring for 1 hr. Then, thestirring was stopped and the reaction was cooled down to roomtemperature and let to settle. The organic layer (insoluble in the ionicliquid) was decanted off and washed with 0.1N KOH. The organic layer wasseparated and dried over anhydrous MgSO₄. The colorless oily substancewas analyzed by SIMDIST. The oligomeric product has a Bromine Number of7.9. Table 1 below shows the SIMDIST analysis of the oligomerizationproducts.

Example 3 Alkylations of 1-Decene Oligomers

The oligomers of 1-decene made as described in example 2 were alkylatedwith isobutane in 1-butylpyridinium chloroaluminate and inmethyl-tributyl ammonium chloroaluminate (TBMA) ionic liquids accordingto the procedures described below. In a 300 cc autoclave fitted with anoverhead stirrer, 26 gm of the oligomer and 102 gm of isobutane wereadded to 21 gm of methyl-tributyl-ammonium chloroaluminate ionic liquid.To this mixture, 0.3 gm of HCl gas was added and the reaction was heatedto 50° C. for 1 hr while stirring at >1000 rpm. Then the reaction wasstopped and the products were collected in a similar procedure asdescribed above for the oligomerization reaction. The collectedproducts, colorless oils, have Bromine Number of 3.2. Table 1 shows theSIMDIST analysis of the oligomer alkylation products.

Alkylation of the oligomer was repeated using the same proceduredescribed above, but 1-butylpyridinium chloroaluminate was used in placeof methyl-tributyl-ammonium chloroaluminate. Alkylation of the oligomerin butylpyridinium gave a product with a bromine index of 2.7. TheSIMDIST data is shown in Table 1.

TABLE 1 1-Decene oligomers 1-Decene 1-Decene Alkylation in 1- oligomersSIMDIST Oligomers butylpyridinium alkylation TBP (WT %) ° F.chloroaluminate in TBMA TBP@0.5 330 298 296 TBP@5 608 341 350 TBP@10 764574 541 TBP@15 789 644 630 TBP@20 856 780 756 TBP@30 944 876 854 TBP@401018 970 960 TBP@50 1053 1051 1050 TBP@60 1140 1114 1118 TBP@70 11921167 1173 TBP@80 1250 1213 1220 TBP@90 1311 1263 1268 TBP@95 1340 12871291 TBP@99.5 1371 1312 1315

Example 4 Oligomerization of 1-Decene in Ionic Liquids in the Presenceof Iso-Butane

Oligomerization of 1-decene was carried out in acidic 1-butyl-pyridiniumchloroaluminate in the presence of 10 mole % of isobutane. The reactionwas done in the presence of HCl as a promoter. The procedure belowdescribes, in general, the process. To 42 gm of 1-butyl-pyridiniumchloroaluminate in a 300 cc autoclave fitted to an overhead stirrer, 101gm of 1-decene and 4.6 gm of isobutane were added and the autoclave wassealed. Then 0.4 gm of HCl was introduced and the stirring started. Thereaction was heated to 50° C. The reaction was exothermic and thetemperature quickly jumped to 88° C. The temperature in few minutes wentback down to 44° C. and was brought up to 50° C. and the reaction wasvigorously stirred at about 1200 rpm for an hour at the autogenicpressure (˜atmospheric pressure in this case). Then, the stirring wasstopped and the reaction was cooled to room temperature. The contentswere allowed to settle and the organic layer (immiscible in the ionicliquid) was decanted off and washed with 0.1N KOH aqueous solution. Thecolorless oil was analyzed with simulated distillation and bromineanalysis. The Bromine Number was 2.6. The Bromine Number is much lessthan that usually observed for the 1-decene oligomerization in theabsence of isobutane. The Bromine Number for 1-decene oligomerization inthe absence of iC₄ is in the range of 7.5-7.9 based on the catalyst,contact time and catalyst amounts used in the oligomerization reaction.The Simulated Distillation data is shown in Table 3.

The Simulated Distillation data in Tables 1 and 3 show that alkylationsof the already made 1-decene oligomers with isobutane and thesimultaneous oligomerization/alkylation of 1-decene lead to fairlycomparable products. The overall outcome of the two operations isamazingly close in the products boiling ranges and olefinic contents asindicated by bromine numbers shown in Table 2.

Table 2 compares the Bromine Numbers of the starting 1-decene, 1-deceneoligomerization products in the presence of iC₄, 1-deceneoligomerization products without iC₄, and the alkylation products of1-decene oligomers with excess iC₄.

TABLE 2 Oligomerization- Oligomeriza- alkylation of tion ProductsAlkylated 1- 1-Decene with of 1-Decene/ 1-decene Material Decene 10 mol% iC₄ No iC₄ oligomers Bromine 114 2.6 7.9 2.8 Number

The data above suggests that the chemistry can be done by eitheralkylating the oligomers in situ (where isoparaffins are introduced intothe oligomerization reactor) or in consecutive step to oligomerizationof an alpha olefin. In both processes, the yielded products are close intheir properties. In the simultaneous oligomerization-alkylation scheme,the desired alkylated oligomeric products can be made in one single stepand, thus, can be economically advantageous process. However, the twostep process with two separate reaction zones where each can beoptimized independently, provides greater chances for tailoring andtuning the conditions to make products with particularly desiredproperties.

Example 5 Oliaomerization of 1-Decene in Ionic Liquids in the Presenceof Varying Iso-Butane Concentrations

Oligomerization of 1-decene was carried out in acidic 1-butyl-pyridiniumchloroaluminate in the presence of varying mole % of isobutane. Thereaction was done in the presence of HCl as a promoter (co-catalyst).The procedure below describes, in general, the process. To 42 gm of1-butyl-pyridinium chloroaluminate in a 300 cc autoclave fitted to anoverhead stirrer, 101 gm of 1-decene and 4.6 gm of isobutane were addedand the autoclave was sealed. Then 0.2-0.5 gm of HCl was introduced intothe reactor, and then, started the stirring. The reaction is exothermicand the temperature quickly jumped to 88° C. The temperature droppeddown quickly to the mid 40s and was brought up to 50° C. and kept ataround 50° C. for the remainder of the reaction time. The reaction wasvigorously stirred for about an hour at the autogenic pressure. Thestirring was stopped, and the reaction was cooled to room temperature.The contents were allowed to settle and the organic layer (immiscible inthe ionic liquid) was decanted off and washed with 0.1N KOH aqueoussolution. The recovered oils were characterized with simulateddistillation, bromine analysis, viscosity, viscosity indices, and pourand cloud points.

Table 3 below show the properties of the resulting oils of different1-decene/isobutane ratios. All the reactions were run for approximately1 hr at 50 degrees C. in the presence of 20 gm of ionic liquid catalyst.

TABLE 3 C₁₀ ⁼/ C₁₀ ⁼/ C₁₀ ⁼/ C₁₀ ⁼/ C₁₀ ⁼/ n iC4 = 0.8 iC₄ = 1 iC₄ = 4iC₄ = 5.5 iC₄ = 9 TBP @0.5 301 311 322 329 331 TBP @5 340 382 539 605611 TBP @10 440 453 663 746 775 TBP @20 612 683 792 836 896 TBP @30 798842 894 928 986 TBP @40 931 970 963 999 1054 TBP @50 1031 1041 1007 10591105 TBP @60 1098 1099 1067 1107 1148 TBP @70 1155 1154 1120 1154 1187TBP @80 1206 1205 1176 1200 1228 TBP @90 1258 1260 1242 1252 1278 TBP@95 1284 1290 1281 1282 1305 TBP 1311 1326 1324 1313 1335 @99.5

The data shown in Table 3 indicate that the amount of isobutane added tothe reaction does influence the boiling range of the produced oils. Asshown in the in Table 3, there are more in the lower boiling cuts athigher concentration of isobutane in the reaction. This indicates thatmore alkylation is taking. part directly with 1-decene and 1-decenedimers rather than with higher oligomers when higher isobutaneconcentrations are present in the reaction zone. When more isobutane ispresent more alkylation can occur, and 1-decene alkylation with iC₄ tomake C₁₄ and 1-decene dimer alkylation to make C₂₄ will be moreprevalent than at lower concentrations of isobutane. Therefore, thedegree of branching and oligomerization can be tailored by the choice ofolefins, isoparaffins, olefin/isoparaffin ratios, contact time and thereaction conditions. The alkylated oligomers will no longer take part infurther oligomerization due to “capping” off their olefinic sites, andthe final oligomeric chain will be shorter perhaps than the normaloligomeric products but with more branching.

While the oligomerization pathway is the dominant mechanism, it is veryclear that the alkylation of 1-decene and its oligomers with isobutanedoes take part in the chemistry.

Table 4 below compares some physical properties of the products obtainedfrom the reactions of Table 3

TABLE 4 C10⁼/ C10⁼/ C10⁼/ C10⁼/ C10⁼/ iC₄ = 0.8 iC₄ = 1 iC₄ = 4 iC₄ =5.5 iC₄ = 9 VI 145 171 148 190 150 Vis@100 9.84 7.507 9.73 7.27 11.14VIS@40 61.27 37.7 59.63 33.5 70.21 Pour −42 −42 −44 −52 Point Cloud −63−64 −69 −28 Point Bromine 3.1 0.79 2.2 3.8 6.1 Number

The oligomerization/alkylation run@1-decene/iC₄ ratio of 5.5 wasrepeated several times at the same feed ratios and conditions. Theviscosity@100 in the repeated samples ranged from 6.9-11.2. The VIranged from 156-172. All the repeated samples contained low boiling cuts(below 775 degrees F.) ranging from 10%-15%. The low boiling cut appearsto influence the VI.

The Bromine Numbers shown in Table 4 are much less than usually observedfor the 1-decene oligomerization in the absence of isobutane. TheBromine Number for 1-decene oligomerization in the absence of iC₄ is inthe range of 7.5-7.9 based on the catalyst, contact time and catalystamounts used in the oligomerization reaction. Table 5 below compares theBromine Number analysis of 1-decene, simultaneous oligomerization andalkylation of 1-decene, 1-decene oligomerization only products, and thealkylated oligomers (oligomerization followed by alkylation). By lookingat these values, one can see the role of the incorporation of isobutaneon the olefinicity of the final products.

TABLE 5 Oligomerization Alkylated with 10 mol % 1-Decene 1-decene 1-iC₄, (20 mol % Oligomeri- oligomers Material Decene iC₄) zation with iC₄Bromine 114 6.1, (2.2) 7.9 2.8 Number

Example 6 Oligomerization of a Mixture of Alpha Olefins in the Presenceof Iso-Butane

A 1:1:1 mixture of 1-hexene:1-octene:1-decene was oligomerised in thepresence of isobutane at the reaction conditions described earlier foroligomerization of 1-decene in the presence of isobutane (100 gmolefins, 20 gm IL catalyst, 0.25 gm HCl as co-catalyst, 50° C.,autogenic pressure, 1 hr). The products were separated from the ILcatalyst, and the IL layer was rinsed with hexane, which was decantedoff and added to the products. The products and the hexane wash weretreated with 0.1N NaOH to remove any residual AlCl₃. The organic layerswere collected and dried over anhydrous MgSO₄. Concentration (on arotary evaporator at reduced pressure, in a water bath at ˜70 degreesC.) gave the oligomeric product as viscous yellow oils. Table 6 belowshows the Simulated Distillation, viscosity, and pour point, cloudpoint, and bromine number data of the alkylated oligomeric products ofthe olefinic mixture in the presence of isobutane.

TABLE 6 Oligomers of SIMDIST C₆ ⁼, C₈ ⁼, C₁₀ ⁼W/iC₄ TBP (WT %), ° F. TBP@0.5 313 TBP @5 450 TBP @10 599 TBP @15 734 TBP @20 831 TBP @30 953 TBP@40 1033 TBP @50 1096 TBP @60 1157 TBP @70 1220 TBP @80 1284 TBP @901332 TBP @95 1357 TBP @99.5 1384 Physical Properties: VI 140 VIS@1007.34 CST VIS@40   42 CST Pour Point  −54° C. Cloud Point <−52° C.Bromine # 3.1

As shown in the data above, high quality oils with desirable lubricatingproperties can be made by either simultaneous olefinoligomerization/alkylation, or by oligomerization of the appropriateolefins followed by alkylation of the oligomeric products. Regardless ofthe process, the oils produced in both processes appear to be close intheir boiling ranges, olefinicity and physical properties such asviscosity indices, viscosities, pour points and cloud points. Bothprocess lead to oils with appreciable concentrations of branchedparaffins formed by capping (alkylating) olefins and their oligomers andlow olefin concentrations.

1. A process for making a lubricant or lubricant component, comprising:oligomerizing a feed comprising one or more olefins in an ionic liquidoligomerization zone comprising an acidic ionic liquid catalyst, atoligomerization conditions, to form an oligomer; alkylating saidoligomer in the presence of an isoparaffin, in an ionic liquidalkylation zone comprising an acidic ionic liquid catalyst, atalkylation conditions, to form an alkylated oligomeric product that issaid lubricant or lubricant component, having a cloud point less than−50 degrees C., a Viscosity Index of at least 134, and a differencebetween the T90 and T10 boiling points of at least 225 degrees F. bySIMDIST.
 2. The process of claim 1 wherein the ionic liquid alkylationzone further comprises a Brönsted acid.
 3. The process of claim 1wherein the mole ratio of oligomer to isoparaffin is at least 0.5. 4.The process of claim 1 wherein sais alkylated oligomeric product has aBromine Number of less than 2.7.
 5. The process of claim 1 wherein thealkylated oligomeric product has a TBP@50(Wt %) of at least 538 degreesC. (1000 degrees F.) by SIMDIST and a Bromine Number of less than
 4. 6.The process of claim 1 wherein said alkylated oligomeric product has aBromine Number of less than
 3. 7. The process of claim 1 wherein theisoparaffin is selected from the group consisting of isobutane,isopentane, and a mixture comprising isobutane and isopentane.
 8. Theprocess of claim 1 wherein the alkylated oligomeric product is subjectedto hydrogenation to produce a low olefin lubricant base oil.
 9. Theprocess of claim 8 wherein said low olefin lubricant base oil has aBromine Number of less than 0.2 by ASTM D
 1159. 10. The process of claim1 wherein the feed stream comprising one or more olefins comprises atleast one alpha olefin.
 11. The process of claim 1 wherein the feedstream comprising one or more olefins comprises at least 50 mole % of asingle alpha olefin species.
 12. The process of claim 1 wherein the feedstream comprising one or more olefins comprises a mixture of alphaolefins.
 13. The process of claim 1 wherein the alkylated oligomericproduct is subjected to hydrogenation to form a low olefin contentalkylated oligomer.
 14. The process of claim 13 wherein the low olefincontent alkylated oligomer has a Bromine Number of less than 0.2 asmeasured by ASTM D
 1159. 15. The process of claim 1 wherein the ionicliquid oligomerization zone comprises an acid chloroaluminate ionicliquid catalyst.
 16. The process of claim 1 wherein the ionic liquidoligomerization zone comprises a first ionic liquid catalyst and theionic liquid alkylation zone comprises a second ionic liquid catalyst.17. The process of claim 16 wherein the first ionic liquid-catalyst andthe second ionic liquid catalyst are the same.
 18. The process of claim1 wherein the ionic liquid alkylation zone and the ionic liquidoligomerization zone are the same zone.